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1.
Summary The FeII, FeIII, CoII, CoIII and NiII violurates have been synthesised and their electronic spectra (in Nujol mulls and dimethyl formamide), i.r. spectra, magnetic properties, molar conductivity, differential thermal analysis (d.t.a.), thermogravimetric analysis (t.g.a.), elemental analysis, m.p., specific gravity and solubility have been recorded. The structures of the complexes have been inferred from magnetic and spectral data.  相似文献   

2.
Polycrystalline Co0.75Ni0.75[Fe(CN)6]?·?XH2O was prepared by coprecipitation. The coprecipitated powder was annealed in vacuum at 80°C, 100°C, and 130°C. Variation of microstructural and magnetic properties with different annealed temperatures was studied by Fourier-transform infrared, X-ray diffraction, and magnetization measurements. The differences in magnetic phase transition temperature, coercivity, remanence, and effective magnetization were studied in detail. The magnetic contribution mainly results from FeIII–CN–CoII/NiII and FeIII–NC–CoII/NiII because FeII–CN–CoIII/NiII carries no net spin. After annealing at 130°C, the microstructures FeIII–CN–CoII/NiII and FeIII–NC–CoII/NiII convert to FeII–CN–CoIII/NiII. Differences in magnetic properties may be attributed to heat-induced microstructural changes.  相似文献   

3.
Summary Complexes of FeII, FeIII, CoII, CoIII and NiII with dinitroso resercinol (DNR) have been isolated and characterised. Ni studies showed that the metals are coordinated to the oxygens of one hydroxyl and one nitroso group, the second hydroxyl and nitroso groups remaining uncoordinated. The magnetic moments of the FeII and NiII complexes are commensurate with tetrahedral (or disorted octahedral) structures, while the others are ocahedral, however, the electronic spectra suggest ocahedral stereochemistries for all the complexes.  相似文献   

4.
A bisamidopyridine-type receptor, N,N′-bis(6-methyl-2-pyridyl)pyridine-2,6-dicarboxamide (1), and its CoIII complex were prepared and their X-ray structures were compared to those of N,N′-diphenylpyridine-2,6-dicarboxamide (2) and CoIII(2)2. Introduction of the two additional coordinative groups resulted in second-order interactions between the central ion and the nitrogen atoms of the terminal pyridine moieties in the crystalline state. Solution studies in acetonitrile revealed the importance of these interactions for the ligand's metal ion recognition ability. Whereas 2 only binds to PbII and CuII, 1 yields complexes with a majority of the heavy and transition metal ions studied, CoII, NiII, CuII, ZnII, FeIII, FeII, HgII, and PbII, respectively. The cation binding properties in solution were investigated by absorption spectroscopy and in the case of 1–MII/III, the formation of two spectroscopically distinguishable types of complexes was found. Protonation experiments and theoretical considerations helped to gain further insight into possible modes of coordination in solution.  相似文献   

5.
FeII, CoIII, NiII, PdII, and RhIII chelates with the N-unsubstituted 1-2-diimine ligands benzildiimine and 9.10-phenanthrenequinonediimine have been prepared. The compounds are characterised chemically, spectroscopically (uv, vis, ir) and polarographically. The results indicate remarkable π-back bonding in the chelates. The unusual magnetic moments of the FeII, CoIII and RhIII chelates are caused by temperature-independent paramagnetism. FeII, CoIII, NiII and CuII chelates of the partially deprotonated phenanthrenequinone diimine are obtained.  相似文献   

6.
A fluctuating charge model for transition metal complexes, based on the Hirshfeld partitioning scheme, spectroscopic energy data from the NIST Atomic Spectroscopy Database and the electronegativity equalization approach, has been developed and parameterized for organic ligands and their high‐ and low‐spin FeII and FeIII, low‐spin CoIII and CuII complexes, using atom types defined in the Momec force field. Based on large training sets comprising a variety of transition metal complexes, a general parameter set has been developed and independently validated which allows the efficient computation of geometry‐dependent charge distributions in the field of transition metal coordination compounds. © 2013 Wiley Periodicals, Inc.  相似文献   

7.
In this study, the Schiff base ligands H2L1–H2L3 and their CuII, CoII, NiII, FeIII RuIII and VOIV complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear. Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form in the C7H8 and C6H14. The C–C coupling reaction of the 2,6-di-t-butylphenol has been investigated by the CoII and CuII complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found. In the FeIII and RuIII complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and CH3CN).  相似文献   

8.
Complexes of CrIII, MnII, FeIII, CoII, NiII and CuII containing a macrocyclic pentadentate nitrogen–sulphur donor ligand have been prepared via reaction of a pentadentate ligand (N3S2) with transition metal ions. The N3S2 ligand was prepared by [1 + 1] condensation of 2,6-diacetylpyridine with 1,2-di(o-aminophenylthio(ethane. The structures of the complexes have been elucidated by elemental analyses, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. The complexes are of the high spin type and are six-coordinate.  相似文献   

9.
From the viewpoints of large capacity, long‐term guarantee, and low cost, interest in magnetic recording tapes has undergone a revival as an archive storage media for big data. Herein, we prepared a new series of metal‐substituted ?‐Fe2O3, ?‐GaIII0.31TiIV0.05CoII0.05FeIII1.59O3, nanoparticles with an average size of 18 nm. Ga, Ti, and Co cations tune the magnetic properties of ?‐Fe2O3 to the specifications demanded for a magnetic recording tape. The coercive field was tuned to 2.7 kOe by introduction of single‐ion anisotropy on CoII (S=3/2) along the c‐axis. The saturation magnetization was increased by 44 % with GaIII (S=0) and TiIV (S=0) substitution through the enhancement of positive sublattice magnetizations. The magnetic tape media was fabricated using an actual production line and showed a very sharp signal response and a remarkably high signal‐to‐noise ratio compared to the currently used magnetic tape.  相似文献   

10.
Summary N-salicylidene anthranilamide (H2SAA) and its CrIII, MnII, FeIII, CoII, NiII and CuII complexes were prepared and characterized by physicochemical and spectroscopic data. H2SAA enolizes to give a dibasic ONO donor set in the divalent metal complexes. It also binds to the trivalent metal ions in a nonenolized form using a monobasic ONN donor set. CoII is oxidized to CoIII during complexation. Octahedral geometries are proposed for CrIII, MnII, FeIII and CoIII complexes, while square planar geometries are suggested for the NiII and CuII complexes. Phenoxide bridging in the CrIII and FeIII complexes and enoxide bridging in the NiII and CuII complexes is proposed.  相似文献   

11.
Summary Benzoylacetic acid (1 mol) interacts with ethylenediamine or with propanediamine (2 mol) to yield new N4 macrocycles 1,5,8,12-tetraazacyclotetradeca-2,4,9,11-tetraphenyl-3, 10-dicarboxylic-4,11-diacetic acid- 1,8-diene (L1) and 1,5,9,13-tetraazacyclohexadeca-2,4,10,12-tetraphenyl-3, 11-dicarboxylic-4,12-diacetic acid-1,9-diene (L2), respectively. These macrocycles have been successfully complexed with CrIII, FeIII, MnII, CoII, NiII, CuII and ZnII. The complexes of the divalent metal ions are non-electrolytes, while those of FeIII and CrIII are 1:1 electrolytes in DMSO. On the basis of ligand field spectra and magnetic moments an octahedral geometry has been proposed for all the complexes.  相似文献   

12.
Complexes of CuII, NiII, CoII and FeIII with Schiff-bases derived by condensing o-aminophenol and ethanolamine with dibenzoylmethane, benzoylacetone, acetylacetone and thenoyltrifluoroacetone have been prepared and characterized by elemental analysis, electrical conductivity, magnetic moment, d.t.a. and t.g.a. measurements, i.r., u.v.–vis., e.s.r. and Mössbauer spectra. All the complexes are non-electrolytes. Those with 1:2 metal:ligand ratios have an octahedral or distorted octahedral environment. Square-planar, Td or D2d structures have been proposed for the 1:1 complexes. The Mössbauer spectrum of the FeIII complex confirms its high-spin octahedral stereochemistry.  相似文献   

13.
A theoretical density functional study of the magnetic coupling interactions and magnetic anisotropy in a family of experimentally synthesized and theoretically modeled M′6M8(CN24) (M′=CuII, NiII or CoII; M=FeIII or CrIII) systems is presented. The calculations show that the interactions in the selected M′6M8(CN24) are all ferromagnetic and the near cubic symmetry of Cu6Fe8 is the origin of its negative magnetic anisotropy parameter D.  相似文献   

14.
Summary FeIII, CoII, NiII and CuII, complexes of a new Schiff base ligand, prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with benzaldehyde (ACB), and also CuII and NiII complexes of a second Schiff base ligand prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with salicylaldehyde (ACS), have been prepared and characterized by elemental analyses, conductivity measurements, magnetic and spectral (electronic, i.r. and e.p.r.) studies. The i.r. spectra suggest that both ACB and ACS are acting as bidentate ligands, coordinating through one of the sulphur atoms and through the azomethine nitrogen atom. The magnetic moment of the FeIII complex indicates spin crossover behaviour. Square planar structures have been assigned to the CuII and NiII complexes and a tetrahedral structure to the CoII complex. The e.p.r. spectra of the CuII complexes suggest a square planar environment with rhombic distortion around the CuII ion.  相似文献   

15.
Seven types of complexes were obtained when penicillin G potassium (pin) was reacted with transition and non-transition metal ions in methanol/distilled water mixed solvent. Magnetic susceptibilities and ESR spectra (CuII complex) of powdered samples indicated that the monomeric form of the complexes in the solid state, and the paramagnetic nature of the CuII, NiII, MnII, CrIII, CoII, and FeIII complexes is attributable to the octahedral ligitional behavior of the potassium G penicillinate ligand. The antibacterial activity of the metal complexes were tested against some kind of bacteria and fungi strains and compared with penicillin G potassium activity. The possible mechanism of antibacterial action is discussed.  相似文献   

16.
The ligand H6ioan has been used to synthesize the three dinuclear complexes [(ioan)MnIITiIV], [(ioan)FeIITiIV], and [(ioan)FeIIITiIV]+. The face-sharing bridging mode of the three phenolates provides short M-TiIV distances of ≈3.0 Å. Mössbauer spectra of [(ioan)FeIIITiIV]+ show a magnetically split six-line spectrum at 3 K in zero magnetic field demonstrating a slow magnetic relaxation. Magnetic measurements provide a zero-field splitting of |D|=5 cm−1 in [(ioan)FeIITiIV]. EPR spectroscopy demonstrates sizable zero-field splittings of the S=5/2 spin systems of [(ioan)MnIITiIV] (D=0.246 cm−1) and [(ioan)FeIIITiIV]+ (D<−1 cm−1) that can be related to enforced covalency of the M-Oph bonds. [(ioan)FeIIITiIV]+ exhibits a reversible reduction at −0.26 V vs. Fc+/Fc demonstrating the facile accessibility of FeIII and FeII. In contrast to an irreversible oxidation in [(ioan)NiIITiIV] at 0.78 V vs. Fc+/Fc, the reversible oxidation at 0.25 V vs. Fc+/Fc in [(ioan)MnIITiIV] indicates even the access of MnIII. These results indicate that pentanuclear complexes [(ioan)FeM1M2M1Fe(ioan)]n+ are meaningful targets to access electron delocalization in mixed-valence systems over five ions due to the facile accessibility of both FeII and FeIII in the terminal positions. This study provides important local spin-Hamiltonian and Mössbauer parameters that will be essential for the understanding of the potentially complicated electronic structure in the anticipated pentanuclear complexes.  相似文献   

17.
A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII2CoII2 square complex into a molecular switch exhibiting a full dia- to paramagnetic transition: FeIICoIII ⇔ FeIIICoII. Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure-enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising-like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.  相似文献   

18.
A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII2CoII2 square complex into a molecular switch exhibiting a full dia‐ to paramagnetic transition: FeIICoIII ? FeIIICoII. Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure‐enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising‐like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.  相似文献   

19.
Summary The chelating behaviour of two biologically active ligands, pyridine-2-carboxaldehyde(4-phenyl) thiosemicarbazone(L1H) and pyridine-2-carboxaldehyde thiosemicarbazone(LH), towards FeIII, CoIII, FeII and RhIII has been investigated. The ligands act as tridentate N–N–S donors, resulting in the formation of bis-chelate complexes of the type MIII(A)2X·nH2O (A=L1 or L; X=Cl, ClO4; M=CoIII, RhIII, FeIII), FeII(L1H)2SO4·2H2O and FeII(L1)2·H2O. Biological activity of the ligands and the metal complexes in the form ofin vitro antibacterial activities towardsE. coli has been evaluated and the possible reasons for enhancement of the activity of ligands on coordination to metal ion is discussed.  相似文献   

20.
Disulfide/thiolate interconversion supported by transition‐metal ions is proposed to be implicated in fundamental biological processes, such as the transport of metal ions or the regulation of the production of reactive oxygen species. We report herein a mononuclear dithiolate CoIII complex, [CoIIILS(Cl)] ( 1 ; LS=sulfur containing ligand), that undergoes a clean, fast, quantitative and reversible CoII disulfide/CoIII thiolate interconversion mediated by a chloride anion. The removal of Cl? from the CoIII complex leads to the formation of a bis(μ‐thiolato) μ‐disulfido dicobalt(II) complex, [Co2II,IILSSL]2+ ( 2 2+). The structures of both complexes have been resolved by single‐crystal X‐ray diffraction; their magnetic, spectroscopic, and redox properties investigated together with DFT calculations. This system is a unique example of metal‐based switchable Mn2‐RSSR/2 M(n+1)‐SR (M=metal ion, n=oxidation state) system that does not contain copper, acts under aerobic conditions, and involves systems with different nuclearities.  相似文献   

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